title: Selective functionalisation of saturated C-H bonds with metalloporphyrin catalysts.
abstract: The recent surge of interest in metal-catalysed C-H bond functionalisation reactions reflects the importance of such reactions in biomimetic studies and organic synthesis. This critical review focuses on metalloporphyrin-catalysed saturated C-H bond functionalisation reported since the year 2000, including C-O, C-N and C-C bond formation via hydroxylation, amination and carbenoid insertion, respectively, together with a brief description of previous achievements in this area. Among the metalloporphyrin-catalysed reactions highlighted herein are the hydroxylation of steroids, cycloalkanes and benzylic hydrocarbons; intermolecular amination of steroids, cycloalkanes and benzylic or allylic hydrocarbons; intramolecular amination of sulfamate esters and organic azides; intermolecular carbenoid insertion into benzylic, allylic or alkane C-H bonds; and intramolecular carbenoid C-H insertion of tosylhydrazones. These metalloporphyrin-catalysed saturated C-H bond functionalisation reactions feature high regio-, diastereo- or enantioselectivity and/or high product turnover numbers. Mechanistic studies suggest the involvement of metal-oxo, -imido (or nitrene), and -carbene porphyrin complexes in the reactions. The reactivity of such metal-ligand multiple bonded species towards saturated C-H bonds, including mechanistic studies through both experimental and theoretical means, is also discussed (244 references).
authors.affiliation: Department of Chemistry, Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Hong Kong. cmche@hku.hk
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
authors.forename: Vanessa Kar-Yan
authors.initials: VK
authors.lastname: Lo
authors.forename: Cong-Ying
authors.initials: CY
authors.lastname: Zhou
authors.forename: Jie-Sheng
authors.initials: JS
authors.lastname: Huang
mesh_terms: D000586:Amination; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D006859:Hydrogen / Q000737:chemistry*; D006900:Hydroxylation; D008665:Metalloporphyrins / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry
chemical_list: D008665:Metalloporphyrins; C030011:carbene; D002244:Carbon; D006859:Hydrogen; D008697:Methane